Synthesis of organic compounds



Nov. 2?, 1951i L. c. RUBIN SYNTHESIS oF ORGANIC COMPOUNDS 2 SHEETS-SHEET l Filed May 5, 1948 @www Nov. 27, 1951 c. RUBIN 2,576,858

SYNTHESIS OF ORGANIC COMPOUNDS 2 SHEETS- SHEET 2 n n W53 ff/7 y L L 'E 6* C INVENTOR.

LOUIS C. RUBIN BY. 3. XM1/ ATTORNEYS Patented Nov. 27, 1951 SYNTHESIS OF ORGANIC COMPOUNDS Louis C. Rubin, West Caldwell, N. J., assignor to The M. W. Kellogg Company, Jersey City, N. J., a corporation of Delaware Application May 5, 1948, Serial No. 25,256

14 Claims. (01.260-4495) This invention relates to an improved method for hydrogenating carbon oxides to produce hydrocarbons and oxygenated organic compounds. The carbon oxides treated include not only carbon monoxide and carbon dioxide but also other organic compounds which contain the carbonyl group, such as ketones, aldehydes, acyl halides, organic acids and their salts and esters, acid anhydrides, amides, etc., and whose reaction with hydrogen to produce other oxygenated cornpounds and hydrocarbons is promoted by the catalysts and reaction conditions which are eifective to promote the reaction of hydrogen with carbon monoxide or carbon dioxide. While the improved process is applicable to the hydrogenation of these compounds of oxygen and carbon, hereafter referred to as carbon oxides, to produce both hydrocarbons and oxygenated organic compounds, the invention is particularly applicable to the large-scale production of hydrocarbons by the hydrogenation of these carbon oxides, particularly carbon monoxide. This application is a continuation-impart of application Serial No. 550,799, led August 23, 1944, now Patent No. 2,448,279.

In reacting a carbon oxide, such as carbon monoxide, with hydrogen to produce a desired product, it is necessary to maintain the reaction temperature at the level at which the reactions leading to the desired product predominate over collateral reactions which form undesired products. Such temperature control is extremely diiiicult because the reactions resulting from the hydrogenation of carbon Oxides are highly exothermic.

It is an object of this invention to provide an improved method for reacting hydrogen with carbon oxides, in which the catalyst is employed in a highly eicient manner, and at a high space velocity, while rapidly removing heat from the zones of highest reaction rate in the catalyst chamber.

The present invention comprises contacting the gaseous or vaporous reactants with finely divided catalyst under conditions such that the catalyst is suspended in the reactants as a dense, pseudo-liquid, turbulent mass in which the catalyst particles circulate at a high rate to produce intimate mixing of the catalyst mass, and removing the heat of reaction, to control the reaction temperature, by injecting into the dense mass of circulating catalyst liquids which are vaporizable at the reaction conditions of temperature and pressure. The mass of -contact material is contained in a suitable reactor, and the reaction gas mixture is passed upwardly through the mass at a velocity which is sufficiently high to maintain the mass of contact material substantially in suspension in the gas. Preferably, the velocity of the gas stream is maintained sufciently low to maintain the greater part of the catalyst mass in pseudo-liquid condition in which it exhibits many of the properties of a true liquid, particularly as to flowability and density. At the same time the velocity is maintained sufliciently high, in the preferred form of the invention, to produce in the relatively dense pseudo-liquid mass of finely divided material a highly turbulent motion ofthe particles, whereby they circulate at a high rate throughout the pseudo-liquid mass.

The "fluidized mass of catalyst is quite dense, resembling in this respect a settled mass of the same material. The density of the fluidized mass ordinarily is not less than half that of the settled mass. While the dense turbulent catalyst mass is said to be suspended in the gas stream, this does not imply any movement of the catalyst mass as a whole along the path of flow of the gas stream. In dense phase operations, the catalyst mass is suspended in the gas stream but not entrained therein, although a portion of the catalyst may be carried away from the dense iluidized mass by becoming entrained in the gas stream emerging from the upper surface or interface of dense pseudo-liquid catalyst mass.

The gas mixture is introduced into the reactor through an inlet in the bottom of the reactor whereby the gas stream passes upwardly through the catalyst mass to be maintained in a iluidized condition. Conveniently the inlet comprises one or more connections whose aggregate cross-sectional area is substantially less than the corresponding dimension of the space in which the fluidized mass of catalyst is to be maintained. The gas stream thus passes into the reactor at a relatively high velocity which prevents the passage of catalyst out of the reactor against the entering gas stream. Inside the reactor the velocity of the gas stream decreases to the rate necessary to produce the desired degree of fluidization of the catalyst mass. For convenience the velocity of the gas stream in the reactor is given in terms of the theoretical velocity of the gas stream through an empty reactor, referred to hereafter as the superficial velocity. It is evident, however, that the velocity of the gas stream decreases to the superficial velocity only if the reactor vis suiciently larger than the volume of luidized catalyst to permit the maximum possible disengagement-of thevgas stream and catalyst.

3 As the concentration of catalyst in the fluidized mass varies from a maximum at the bottom to a minimum at the top, the linear velocity of the gas stream would normally decrease as it passes upwardly through the catalyst mass even without reaction. The extent of the variation in the density of the uidized mass is affected by the superficial velocity, the greatestA variationV inthe density of the catalyst mass being observedat relatively high superficial velocity. The linear velocity of the gas stream is aiected also by thevv contraction in volume of reactants asthe reaction proceeds and by the expansion of Vaporizing cooling liquids. Thus the: superficial velocity at the top of the reactor maybe greater or. less.;

than at the bottom.

If the catalyst chamber or reactor issomewhat.;

larger than the volume occupied by the fluidized mass, the catalyst in the reactor appears.A tobe distributed in two visually distinct phases. The first of these is the .relatively dense, pseudo-liquid mass of luidized catalyst;A previously described; which occupies the lower portion of the reactor and comprises all butaminor proportion of the catalyst inthe reactor. This phase is designated as the dense phase. The second phase, which occupies the upper part of thereactonis a diffuse phase in which the concentration of. contact material is far less, and of` a. diierent order; of magnitude, than thev average concentration, in the dense phase. The diffuse phase may bey said to be a disengaging zoneinvwhich the solids lifted abov the dense phase by the gas stream are disengaged therefrom tothe extent that suchl solids are present in excessA of; the carrying capacity of the gas stream at the minimum velocity reached by the gas stream in the reactor. In the diiuse phase, the concentration of catalyst material-in the gas stream decreases as the latter flows upwardly to a minimum which approaches the carrying capacity ofV the stream-at thesupercial velocity. Between the dense phase of high; concentration and the diffuse phase of lowconcentration there is a relatively narrow zone in which the concentration of solids changes in: a short space from the high concentration of the dense phase to the low concentrationgof" theydiffuse phase. This zone has the appearance'of aninter.- face between two visually distinct-.phases.-

While the dense phase-.operations of-thislnvention includes within its scope operations' involving contact material .having suicientlylarge particle size such that substantially no part of the contact material is carried by entrainment in the-gas stream at the supercial velocity. thezpreferred method of operation involves ordinarily` the use of contact material and operating conditions. such that a portion of the contactmaterialis carried by entrainment in the gas stream atthe superficial velocity. This results from the factthat finely divided contact materials are desirableas presenting a greater ratioof surface to volume and affording the maximum efciency of heat transfer between particles and the further fact that suicient mixing of a catalyst mass of substantial cross-sectional areaordinarily requires the use of superficial velocities which entrain a portion of the finely dividedv contact material in the gas stream, In this preferred method; of: operation mere settling is not suflicientto disengage all the catalyst from the gasl stream emerging from the dense phase of the. catalyst` mass. Hence it is necessary to provide means 1inY the reactor to separatel entrainedl catalyst;`fro1n the gas streamer replenish the catalyst-.masszbyL intermittent vor continuous addition of finely divided catalyst to the reactor. Catalyst to be added to the suspended mass may be entrained in the entering gas stream and thus carried into the reactor or it may be added directly to the reactor at a point above the gas inlet. The catalyst thus charged to the reactor may comprise fresh contact material or catalyst previously carriedl out of the reactor by entrainment. Catalyst thus recovered and returned may be subjected to any appropriate treatment after recovery.,.s.uch. as cooling, dewaxing and revivification or regeneration.

The gas-.stream is withdrawn from the top of the. reactor` through an exit which is ordinarily ofA substantially smaller cross-sectional area than thereactor. This provides a high velocity outlet for the gases which is surrounded by an area in which, the. gas velocity accelerates. The nearer this zone of accelerating gas velocity is to the densephase, the greater is the concentration of solids in the gas stream entering the zone and thegreater. is the quantity of solids which must be recovered from the exit stream or separated bymeans inthe reactor.4 The quantity of catalystin the outlet approaches the carrying capacity of the high velocity exit gas streamwhen it is desired to maintain the upper level of thefdense phase. in the vicinity ofthe zone of, accelerating velocity. This quantity will be equivalent to the quantity of catalyst.; introduced into the reactor whenthe dense phase` extends to the outlet and whencatalyst is not withdrawn by other means, such. as a standpipe. l

Inthepreferred method of operation the reactor is. made suiciently larger than the required volume of dense luidized catalyst mass to vprovide a relatively large. diluteV or-diffuse phase in which substantial disengagement ofcatalyst from the gasstream occursbysettling. This disengagement of'catalysty is4 aided by. injecting a suitable liquid, preferablysubstantially free from solids, directly into this dilute phase. The residual amount. off catalyst still carried by entrainment is recovered from the gas stream outside the reactor, or separating. means. are provided in the reactor.

Inl accordance with this invention the turbulent masst of'suspended catalystin the dense phaseis maintainedE at the'desired reaction temperature level by directly injecting into the dense phase liquids which are vaporizable at the reaction conditions of temperature;l pressureand concentration. Similarly; in a preferred embodiment of the invention, liquid is injected into theV dilute phaser above thedensefphasel to quench the gases passing-from thedense phase. The quantity of such injectedliquids and1tlie distribution thereoi.l the4 reactionzone in either the dense or dilute phase are controlled to produce substantiallyy instantaneous vaporization of: the liquids whereby the formation of agglomerates in the catalystmassiothe-dense phaseis avoided. In operations which producev a high degree of turbulence-inpthecatalysttmass whereby the catalyst particles circulate at a` relatively high rate the. liquids; may, be injected into substantially any part;-y of"the; dense phase. If the conditions of operationsaresuch that circulation of the catalyst;.isfeiectedf to a lesser degree it is necessary toconcentrate the injected liquids in-that portion of thedensevrphase in-vvhich the reaction is proceedingv at. the greatest rate.- The liquids which are vaporized-in this manner are withdrawn from the;V reactionY zoneV with. the vaporous reaction products and unreacted gases andare separated from the reaction products externally of the reactor.

In this improved method of operation there is no necessity for removing catalyst material from vthe reactor in excess of the quantity which it may be desired to remove for revivilcation treatment or for the removal of waxy products therefrom. It is desirable, therefore, to maintain a relatively large disengaging space above the dense phase in the reactor and to inject. a suitable liquid into this disengaging space to cause substantial separation of entrained contact material from the gas stream in the reactor. The amount carried overhead by entrainment may be limited to the quantity which is desired to Withdraw for external treatment or the quantity removed by entrainment may be reduced to the minimum, by proper adjustment of the variations discussed above, and the catalyst withdrawn from the reactor for revivilcation or wax recovery may be removed directly from the dense phase at a lower point in the reactor.

The use of gas velocities sufliciently great to entrain substantially all of the catalyst whereby the catalyst particles continuously move in the direction of flow of the gases is within the scope of this invention. In such method of operation, the catalyst and gases pass together from the reaction zone. The catalyst is then separated from the eluent gases and is recycled to the reaction Zone.

The liquid which is injected to control the temperature in the reaction zone necessarily is one which is substantially completely vaporized at the reaction conditions of temperature, pressure and concentration. The simplest and most available liquid for this purpose is water but the use of water may be undesirable in some instances because of an adverse effect on the catalyst mass by the water. Preferably the cooling liquid should be non-reactive with the catalyst and for this reason it is satisfactory ordinarily to employ a portion of the liquid product of the process, particularly when such liquid product is in a highly saturated condition. For example, in the hydrogenation of carbon monoxide to produce a hydrocarbon mixture a light naphtha produced in the process may be employed as the cooling liquid. This material is then recovered inthe product recovery system and returned for reuse. Instead of the light naphtha a higher or lower boiling fraction may be employed. Alternatively, similar materials obtained from any source may be employed. In the selection of a cooling liquid from an external source it is necessary to avoid the introduction of deleterious compounds, such as sulphur compounds, which may injure the catalyst. For this reason a liquid produced in the process is highly desirable as the cooling fluid.

To produce the turbulent pseudo-liquid condition in the dense phase it is desirable that at least a substantial proportion ofthe mass of contact material consist of particles whose free settling rate is less than the supercial velocity in the reactor whereby they are capable of being entrained in the gas stream. The mass of contact material may consist advantageously of a mixture of particles varying in size from 40 to 400 microns (average diameter). However, particles of larger or smaller diameter may be present. The catalyst mass may consist entirely of particles of a single catalytic material or a mixture of particles of different catalytic properties may be employed. For example, finely divided inert materials, such as alumina, bentonite, etc., may be included in the catalyst mass toaid in the iiuidization of the catalyst and as a means for absorbing and dispersing heat.

The catalysts employed include those which promote the reaction of hydrogen and carbon oxides and which can be prepared in a physical condition suitable for the special manner in which the catalyst is to be employed in the improved process. Cobalt, nickel, and iron, with or without suitable supports and promoters, may be used. While kieselguhr has been found to be a superior support in xed bed processes involving this reaction it now appears that clays are superior in the fluidized process. A catalyst cornprising a major proportion of bentonite clay support in combination with cobalt and a minor proportion of a promoter such as thoria, manganese oxide, or magnesia has been found to be satisfactory. Bentonite is available commercially in the form of hydrogen montmorillonite under the names Filtrol and Superflltrol and is obtained by acid treating bentonite.

The ratio in which the carbon oxide and hydrogen reactants are present in the mixture charged to the reaction zone may be varied in accordance with the character of the catalyst and the properties desired in the product. In the hydrogenation of carbon monoxide the hydrogen and carbon monoxide may be charged to the reactor in ratios which have been found satisfactory in previous fixed-bed operations. Ratios of H2:CO in the range of 1:1 to 2:1 are usually employed.

The operating conditions are generally similar to those employed in previous fixed bed operations. The gas stream may be passed through the reactor at a superficial space velocity of 10D-1060 volumes (measured at standard conditions of temperature and pressure) of gas per hour per volume of uidized dense catalyst phase. The temperature employed is affected largely by the nature of the catalyst. Cobalt and nickel catalysts usually are employed at S50-400 F. while iron catalysts require temperatures of 45o-600 F. The pressure employed may vary from atmospheric to super-atmospheric pressures which do not produce condensation in the reactor.

'Ihe invention will be described in more detail by reference to the accompanying drawings and by reference to specific operations embodying the invention. In the drawings Fig. 1 is a diagrammatic representation of an arrangement of apparatus for carrying out the invention and Fig. 2 is a view in elevation, partly in section, of the reactor employed in the specic operations which are described.

Referring to Fig. 1 the reactor i9 is provided with a quantity of powdered catalyst which, upon being fluidized by the passage of reacting vapors upwardly therethrough, forms a pseudo-liquid dense phase in the lower part of the reactor. The charge gas comprising, for example, hydrogen and carbon monoxide and in a usual ratio, is introduced into the lower part of reactor lil through line Il which is provided with a compressor l2. The dimensions of reactor Hl and the quantity of catalyst are regulated whereby the suspension of the catalytic contact material in the stream of gas introduced through line Il produces a dense phase whose upper surface is sufciently low to leave a substantial disengaging space above the dense phase. The upper level of the dense phase, that is, the interface between the dense phase and the diffuse phase in reactor l0 is indicated at agsizeaiss I. Innaccordancezwith thepreferredfmethod of; operating.. the invention .a substantial` separation of i entrained. catalyst: occurs. in the-1 areaabove the dense phase whereby the quantityrofscatalyst carried from thereactor inzthefhigh .velocity exit stream is restrictedi to a minimumg. The` high velocity exit.v of: the. gas is. provided by line?r I4 whichv connectsnat t. one end.'` with thea-upper; partV ofreactor` I' and leads.y to suitable'y separating means, such asa cyclonev separator. I5.Y

The. reacting.. gases'. enter. reactorf I0:` through line I'I at a. high velocity: suchA that@ the finely divided catalytic material in reactor f I 0: doespinot passdownwardly fromv reactor. I0 intot liner Il; 'lhe'initialcharge` of catalyst orsmake-up cata.- lystmay be introducedinto reactor IO-,byentrainingitin the gas stream in line Il', from line Ha. As the reactants enter reactorv lrfrom line IzI there isl a substantial decreasev inl the upward velocity of the gases. The rate at.which1thevref actants are charged to reactor i-is regulatedzvto provide in reactor lo.' anrv upward velocity which suspends the catalyst mass in the gasstream and provides a high degree of mixing. of the catalystmass whereby catalyst.' particlesV circulate throughoutV the dense phase. The vaporous'ref actants may be introduced'throughliner I IT into reactor I 8 at a relatively lowtemperature whereby theyy areheated to the reaction temperature .by contact with the hctcatalyst which is circulating in reactor i; In initiating the operation'the catalyst may be brought'to the reaction tempera-.- ture byztemporarily preheating the' charge gas, as by the provision of heating means I6. After the initiation of the reaction, preheating' of the charge gas at I6 may be unnecessary and even undesirable'.

As the reactants and reaction products emerge from the dense phase at the'interface |31; they. pass upwardly throughthe remainder ofreactor if I9 at a still lower velocity in which entrained'catalyst is separated out ofthe gas stream. Preter erably the height of the reactor issuicient` to permit disengagementl or entrained catalysty to the point where the concentration ofv catalyst zin the gas streaml is reduced to an amountiothe orderv ofv magnitude of 1 the` carrying capacity` Yof the gas stream at the superiicial velocity.:

The mixture of reactants, reactiont products and 'remaining entrained 'catalyst passes through line I4 into the cyclone separator iE inwhicha substantial proportion of the entrained catalyst is'separated. The catalyst thusseparated at` i5 is returned directly. to reactor I0 by' means ofa suitable dip-leg IT which` extends downwardly into the reactor toa point below interface; I3: Preferably the lower end of dip-leg` I7' is'v turned up as shown to minimize the passage of reacting gases into dip-leg IT. The catalyst owing downwardly in dip--legv I'Imay be aerated if'necessary by the injection of inertgases, such as steam, by means not'shown.

The gas stream emerges; from. separator" I5 through line i8 which connects-with ai second catalyst-separator I5 similar=inconstruction and arrangementto separator I5; Inseparatorr |9za further separation of entrained 'catalyst'iseffected andsolids thus separated Yare. returnedxto reactor Ill through dip-leg 2.0, also; terminating below interface I3.

As the reaction of hydrogenand carbon oxide is highly exothermic and as it is'l necessary to maintain the reaction zone, that is'l thefdense catalystphase below interface I;3,` atV thev tem*- peraturelevel whichk promotes the formation-oi thedeslredsproduct; ritzis necessary tot remove. the heatiof reactionfronr.thezreactionv zone'as it is developed. In accordance with this invention the removal ofheatzfrom the reaction zoneis eiiected by.` the'iniection of; liquids whichare vaporized by. the. heat. of.. reaction. This provides. for substantially uniform.=. temperature conditions throughout :the .dense phase whichconstitutes. the reactionzonebecause thehigh rate of circulation of catalystzinthe dense phase permits. effective heat exchange-betweenmt catalyst 4particles and particles whichihavevbeen .cooled byv evaporating liquid.

In accordance. with the` preferred' modiiication ofl this invention anrelatively light oilproducedzin the processis employed as the cooling fluid. It will beunderstood, however, that this primarily for. convenience. since a. suitable liquid'rom. anyvsource may.: be employed. Such a'. liquid is supplied from the system through line 2.1i` which connectswith a distributingheader 22. As'thereaction is most intense near. the entrance of the reactants the development of heatpby. the reaction occurs largely in the lo'werpart of the dense phase. Consequently header 22'is located ator nearthe place in the lower part of the dense phaseat which production of heatis greatest. However, it may be desirable tointroduce cooling liquid at a higher. point in the dense phase insteadoi, or in additionto, the introduction of liquid in the lower part oi'thezdense: phase. For example, a branch line 23 may be provided to connectvr line 2'I. with .an distributing header 2d. located. in the upper part ofthe dense phase. It may be preferable to introduce the cooling liquid at- 24" in order toravoid` any suppression ofv the reaction which might occur through over cooling the catalyst'particlesin the zone of greatest reaction rate.

Alternatively, allor apartofV the cooling liquid may be introduced' through au suitable spray header 25' which" is located above and adjacent thedense phase. Header 25 is connected with linely byxmeans of suitable branchline 25a. Introduction of liquid through header 25u' above the dense phase aids in separation of .catalyst from the gases issuing from` thedense phasev and quenches the reaction. Injection of liquid at this pointinsuicient quantity reduces materially the amount of` entrained catalyst in line Ill. Vaporization ofthe liquid'atthis point quenehes the reaction so that' an accurate reaction time of the reactants isiachievedby regulating the height ofinterface |3.and the gas Velocity which minimizesthe production of normally gaseous organic compounds. Since one.` of the functions of the liquid injected'through header 25 is to aid'in the disengagement of' entrained catalyst, it is preferred that the liquid be substantially free of solids, such as fresher recycled and recovered catalyst.: When-r t-hef cooling liquid contains a substantialamountofi'solids, the liquid or slurry is preferablyinjected' into thev dense phase.

The. quantity of` cooling liquid introduced throughheaders 22,124- and 25is regulated to the amount. which will evaporate completely-in the reaction zone; Preferably also the liquid employe-dtisione which vaporizes readily at the reaction conditonswherebythe time of residence of liquid in contact withA the` catalyst mass is limited.. In thismanner agglomeration of the catalyst yparticles isy avoided. The vaporized cooling liquid passes. overheadv 4with the gas. stream owing through. line I4:

The gas; stream comprising4 unreacted` gases,

such as hydrogen, vaporous and gaseous products, including hydrocarbons and oxygenated organic compounds and Vaporized cooling liquid together with any residual quantity of entrained catalysts flows from separator I9 through line 26 which connects with the lower part of a combined catalyst scrubbing and fractionating tower 21. Tower 21 is divided by a trap-out tray 28 into upper and lower sections. The lower section is operated primarily for the removal of entrained catalyst and condensation of heavy oil constituents of the product. While some fractionation may be effected the baies 29 are arranged primarily to effect intim-ate contact of gases with a circulating liquid stream which ows downwardly over the bailles in contact with the upwardly rising column of gas. In this manner entrained catalyst is separated from the gas stream by condensation of liquids in the gas stream and by the scrubbing action of the circulating stream of liquid. The slurry which forms is recirculated from the bottom of tower 21 through line 3D to a point in tower 21 just below tray 28. Condensation and fractionation is afforded by heating the slurry in the bottom of tower 21 by heating means 3| and by cooling means 32 the stream of liquid circulating through line 33. A pump 33 is provided in line 30 to circulate the slurry.

In the upper part of tower 21 temperature conditions are regulated to eiect separation of a condensate consisting of the liquid product boiling above the gasoline boiling range. Suitable gas and liquid contact means are provided to assist fractionation. The condensate collects on trap-out tray 28 and is withdrawn as a product of the process through line 34. This product is designated for identication as a gas oil but it is understood that its boiling characteristics are affected by the amount of the oil product which is separated as a condensate below tray 28. It will be understood furthermore that the separation of this fraction is merely illustrative of the recovery of an intermediate liquid product. It is evident that means may be provided for fractionating the liquid product into any desired number of fractions.

The uncondensed gases and vapors pass overhead from tower 21 through line 35 which connects with a separator 36. The gases and vapors passing through line 35 are cooled by condenser 31 surciently to effect substantial condensation of the liquids and higher boiling gases such as those having three or four carbon atoms per molecule. This condensate separates from uncondensed gases in accumulator 36- and a portion of the condensate is returned to tower 21 through line 38 as reflux. In this manner the upper part of tower 21 is cooled to produce the desired condensation of higher boiling liquids. Rectication is provided by the hot vapors passing upwardly through tray 23 which heats the condensate collected thereon suliiciently to strip gasoline constituents therefrom. If the heating provided by this means is insuhcient suitable heating coils or reboiling means (not shown) may be provided on tray 28.

The uncondensed gases separated at 36 are withdrawn through line 39 which connects with the bottom of an absorber 40. In absorber 40 the gas stream is contacted with a descending stream of a hydrocarbon oil absorbent. This oil may be any suitable hydrocarbon oil, such asa product of the process of the nature of a gas oil or heavy naphtha. This operation serves to scrub from the gas stream remaining light hydrocarbons which it is desired to include in the liquid product. The scrubbed gases comprising unreacted hydrogen, carbon dioxide and C1 and C2 hydrocarbons are withdrawn from absorber 40 through line 4l and may be recycled to reactor I0 with or without removal of carbon dioxide by conventional means. The enriched absorbent is withdrawn from the bottom of absorber 40 through line 42 which connects with the top of a stripping tower 43. The enriched absorbent may be preheated during its passage through line 42 by heat exchange with lean absorbent at 44 and by conventional heating means 45. In stripping tower 43 the enriched absorbent is further heated by the application of heat through coils 46 in the bottom of tower 43 sulciently to vaporize the light hydrocarbons absorbed in tower 40. Suitable gas and liquid contact means are provided in tower 43 to assist in the separation of the absorbed hydrocarbons and the absorbent. 'I'he stripped absorbent is returned to tower 4l] through line 42a, by pump 43a, during which passage it is cooled by heat exchange at 44 and by cooler 45a. The vaporized light hydrocarbons comprising Ca and C4 hydrocarbons pass overhead from tower 43 through line 41 through which they'are returned to separator 36 by means of compressor 48. Substantially complete condensation of these hydrocarbons is effected by cooling means 49.

The condensate comprising C3 and C4 hydrocarbons and hydrocarbons boiling within the gasoline range accumulated in separator 36 may be withdrawn as a product of the process through line 50 provided with a pump 5|. In accordance with one modification of the invention this oil may be employed as the cooling fluid in reactor Ill. For this operation line 2| is connected with line 50 as shown and a portion of the oil flowing through line 50 is diverted for injection into reactor lll in the manner described above. The use of condensate from separator 36 as the cooling medium is particularly desirable because it boils Within a range which is completely vaporizable in reactor I0 and contains a minimum quantity of undesirable high-boiling compounds.

The slurry which is circulated through the lower portion of tower 21 and line 341 continuous- 1y receives accretion of oil and catalyst from the incoming reaction product. Consequently a Dortion of this slurry is diverted from line 33 through line 52 and passed to a settler 53. In settler 53 the slurry is treated to separate the greater part of the oil from the solid catalytic material. The oil is separately withdrawn from settler 53 as an upper phase through line 54 as a product of the process. Separated solid catalyst is withdrawn from the bottom of settler 53 through line 55 in which it is mixed with light oil to form a slurrv. Oil for this purpose is transferred from line 50 to line 55 by means of line 56. The reconstituted slurry is pumped through line 55 bv means of pump 51 into reactor l() in a suitable point. In this manner the catalyst separated at 53 is returned to the reaction zone for further use, as a slurry in which the vehicle is a portion of the light oil ordinarily injected into reactor IU as a cooling fluid. The liquid component of the slurry introduced into reactor I0 through line 55 is quickly vapoized and the solid component of the slurry is converted to its former condition as a substantially dry catalytic material which is readily dispersed in the dense phase of the catalyst zone in reactor I U.

While the liquid product of the process recov-a lly ered at 50 is entirely suitable for use as the cooling 'fluid and for reslurrying the recovered catalyst it will be understood that these functions may be performed by the same or diierent liquids obtained from an external source. The sole requirement of the cooling iiuid is thatis shall be readily vaporized at the reaction temperature whereby agglomeration of the catalyst particles is avoided.

Instead of employing the wide boiling fraction represented by the product recovered at B it may be desirable to employ a relatively narrow boiling fraction obtained as a product of the process. To obtain such a narrow boiling fraction the liquid product owing through line 5E] may be diverted through line 58 into a debutanizer vtower 59. In tower 59 conditions of temperature and pressure are regulated to separate a bottom product comprising a debutanized gasoline which is withdrawn through line B, and an overhead product consisting essentially of light hydrocarbons having three and four carbon atoms per molecule. An intermediate fraction of relatively narrow boiling range is separa-ted as a liquid condensate on trap-out tray Si which is located at a suitable point in tower 59 above the charge point. The condensate thus separated ls withdrawn through line 52 which connects with line 5l) in the manner shown for passage into lines 55 and 2l. Cooling means 53 may be provided in line 55 as shown to precool the cooling liquid to .any desired temperature.

The gases passing overhead in tower .59k are withdrawn through line S which connects with reiiux drum S5. Cooling means are provided at 56 to effect substantially complete condensation of the gases. The condensate thus obtained is separated in drum 55 and a portion is returned to tower 59 as reflux through line 6l, the remainder being Withdrawn as a product of the process comF prising C3 and C4 hydrocarbons through line $3. Uncondensed gases separated at drum 65 may be passed to absorber 4l? through line 69 which connects drum 65 with line 39. rlhe condensate in line 58 comprises a substantial amount of unsaturated hydrocarbons and consequently it is desirable to pass this fraction to a conventional polymerization unit to polymerize the unsaturated low-boiling hydrocarbons to higher boiling hydrocarbons. The polymerized C3 and Ci hydrocarbon fraction is then blended with the gasoline fraction in line 5G to increase the yield and qual-` ity of the gasoline product.

Instead of the relatively light oils inlines 50 and 52 a heavier oil such as the gas oil in line 3d -or the oil in line 5e may be employed, by means of suitable connections, not shown, as the cooling oil.

Water formed in the reaction will separate as a lower liquid phase in separator 36 and/or settler 53 and may be withdrawn therefrom by means not shown.

rlhe invention will be described in further detail by reference to specific operations carried out in the small scale reactor illustrated in Fig. 2. In Fig. 2 the apparatus is shown in four sections which are joined at A-A, B-B and C-C. The apparatus of Fig. 2 consists essentially of three parts, which are a reactor l5, a shell 'H enclosing reactor l5, and catalyst iilter means 'i2 which surmounts reactor l0. Reactor 'i6 is an elongated cylinder connected to a high velocity inlet pipe 'i3 by means of conical member lli. Jacket ll, which extends from a point near the top of reactor lll to a point sufciently low to enclose a this pipe being enclosed by jacket ll.

- inches.

substantialy length of pipe '13, is adapted to contain a body of liquid, such as water, or Dowtherin This temperature control liquid is maintained in the annular space surrounding reactor 'le under pressure such that it boils at the temperature necessary to maintain liquid to produce the desired reaction temperature. The vapors which are evolved by the heat of reaction are withdrawn through pipe 'I5 at the top of jacket ll. Pipe l5 connects in turn with condensing means, not shown, in which the vapors are cooled and condensed and from which they are returned to the jacket 'Il through pipe l5.

rEhe remaining portion of the apparatus of Fig. 2, located above reactor and in communication therewith, is the catalyst filter means i2 which is provided to separate catalyst which is carried upwardly out of the dense phase in reactor lil. The upper end of reactor 19 is connected by a conical member 15 with an enlarged conduit il. This provided for an enlargement of the path of ilow of the gas stream emerging from the reactor, with a corresponding decrease in upward velocity whereby partial disengagement of solids from the gas stream is effected. Conduit 'il is connected by a manifold 'i8 with conduits "iS and 36, which are similar in construction and diameter to conduit ll. Each of conduits l5 and 83 is provided with an internal filter which is illustrated at 8| in the portion of conduit shown in section. Filter 3l is constructed of porous material which is permeable to the gases and vapors passing from reactor l!) but impermeable to solids carried by entrainment therein. Filter 8| is cylindrical in shape and closed at the bottom end. It is dimensioned in relation to conduit to provide a substantial annular space between the outside of filter 8l and the outside Wall of conduit 35 for the passage of gases and entrained catalyst upwardly about the outer surface of filter 8l. The upper end of lter 8l is mounted in closure means 82 in a manner whereby the gases and vapors from reactor lll must pass through filter 8| to reach the exit pipe 83. Asimilar lter is similarly arranged in conduit 19.

The principal parts of the apparatus of Fig. 2, aside from filters, are constructed of extra heavy steel pipe. Reactor 10 comprises a 153 inch length of extra heavy 2 inch steel pipe having an inside diameter of 1.94 inches and an outside diameter of 2.38 inches. Pipe 13 comprises extra heavy half inch steel pipe having an inside diameter of 0.55 inch, approximately 5 inches of The conical member 'M is approximately 3 inches long. Jacket 'll comprises a length of extra heavy 4 inch steel pipe having an inside diameter of 3.83 inches. Pipe 'l5 consists of extra heavy 2 inch steel pipe. The ends of jacket 1| are formed by closing the ends of the 4 inch steel pipe in any suitable manner as shown. Conduits l?, 'E9 and 30 and manifold l are formed of extra heavy 5 inch steel pipe having an inside diameter of 5.76 The total length of the lter assembly represented by these conduits and member l is 6l inches. The filter 8l is approximately 3 feet long and approximately Li1/2 inches in outside diarneter, the walls of the lter being approximately 3A of an inch thick. The high velocity outlet at 83 is provided by more extra heavy half inch steel pipe.

The injection of cooling fluids into reactor l@ is provided for by nozzles 84, 85 and 3G, which are located 18. 66 and 120 inches, respectively,

Ytively rsmallfscale .apparatus ,of Eig above thelowerfendof reactor 1i), whichgisnthe juncture lbetween"reactor y'H'l and vconical :member .1.1L Nozzles, frand consist of steelftub- Ling-having aniinsidediameter .of approximately :50.'3 inch andzhaveian'orice .of/abouti-groian inchfin diameter.

`,The catalyst filter .means yprovidedby. flter f8 I and .the corresponding '.elementlin conduit -1 9 f; provide substantially @complete separation fof .en-

trained finely' dividedzcatalytic: material from the outgoing streamfof vapors and-gases. Theaiilters in conduits .19 .and f8!) aref-employedialternately The; filter :which: is @notzin lated on the outer surface of.A the lterduringrthe yprevious vperiod :of :use This treatment Vcern- ;prises owing a'gas stream inwardly through-the .usual exit pipe-and through-thelterinthereverse of the iusual direction. The Afg-as stream employed for thisr purpose :flows cutfof i theilter into the conduit and i downwardly vinto -manifo'ld 18. At that point the downflowing gas combines with the upflowingstreamf'ofzreactants from conduit 11 and the combined stream passes upvvardly finto: contact with fthe iilter fin' use. fAny 'substantially inert :gas may be fempleyed for blowing back -ithei lter'ibutlitis convenient Ito employ a portion of the 'vuncondensedend gas from vthe process.

In the operation of the apparatus of Fig. 'Zfthe desired quantity of finely divided solid catalyst is introduced into .reactor .10 through a suitable connection, not shown, to conduit 11. The catalyst preferably ispreheatedtothe reaction temperature prior'to'the contactMof reactants therewith. This maybe v:accomplished by heating the temperature control iiuid injacket 1I to the desired temperature or by passing hot inert gas through reactor '10. Alternately the catalyst may be given thenal reducing treatment after introduction thereof into the reactor by the passage of hot hydrogen thereover. This is sufcient to preheat the catalyst.

The reacting .gasesmay beiintroducedfthrough pipe 13 at the reaction temperature forsat 1=room temperature or atv higher 1 or lower Itemperatures.

.If the reactantsflow through pipe T11:3 :I atfaitemvperature lower than `the vreaction temperature 'they arezpreheated"ordinarilypriorto actual contact'with the catalystfto va temperaturenean the reaction temperaturebymeat exchange :with'ithe temperature, control fluid vin jacket'lz1il .'orftheyfare preheatedin Ithe lower'ipart'of reactor 1.6) by 'con- 'tact'with hot catalyst circulating=from anupper :parttof Vthe reaction zone.

In the 'apparatus 'of Fig. :2 the temperature vcontrol means provided by :j acket'L'Hrand thertem- .perature control fluid therein 'are provided 4'Lto illustratethe use Vof this-.methodof removingtthe heat of reaction in combination withfthefdirect injection :of "vaporizable .cooling rfluid :through lurthermoretin41 thesrela- .the 1 use :of ljacket 1l `and Athe liquid contained therein :is helpful'inisimulating the conditions which exist in a `much larger commercial :installation In` the single tube'apparatus ofthe sizeshcwn .in Fig. 2 the ratiorofrradiating surfaceito ivolumerof the reaction :zone lis muchlhigher vthan would be the case in a largeinstallation. .'Consequently, jacket 1i is helpful 1in keeping Vfthera'diation Vil() 14 llossesLofzthefapparatus ,equivalent to lthose'which would be .encountered lin a Ylarger apparatus. AHeating.meansrnot shown,` are'. .provided :..to'heat l,he liquid in:jacket 1.l Sito :any .desired :temperal ure.

.The :reaction :mixture is `passed r.into `vthe Vap- ;paratus :of Fig.. 2 jthrough .pipe 131ata velocity :such fthatthe :.catalystis liftedaout of pipe 13 vfand maintainedinsuspension in reactcr i10. ./A `ball check valve,'not shown, is providedin pipe f1.3"to prevent catalyst from dropping xcompletely out ofthe reactor When -thegas'f-stream isinot being introduced through pipe 13. The gas stream is passed into pipe 13 at a velocity effective to aerate the catalyst mass in reactor 1U and suspend 'it in the 'gas stream therein. `In the conditions described generally above, in which the lower part of the reactor is occupied by the dense phaseof the fluidized catalyst massand in ".Whichthe upper part of the reactor is "occupied ,by the diffuse phasefthelower boundary of the Asuspended catalyst mass is located lsomewhere 'lb'etween the upperandlovver boundary of coni- 'cal member 14. The upperboundary of the dense Vphase of the catalyst mass is determined-by the @superficial velocity of the gas stream .and `the fquantityiof catalyst charged to the reactor.

Example .'I

--Size Range Weler 40+ j o. o 10A/60 45. 2 60/80 22. 8 80/100 6. 7 1GO/120 4. 8 12o/140 L3 14o/20o Y 5. 7 20D/pali 10. 5

This :catalystfhad `the .ffollowing approximate c ompositionlin parts Lby .Weightc Co 0.15 Mg()I :2 .0 'Superltrol ...Reactor .1t `was purged by ameansof :C62 .and .whileraesmall stream of CO2 was `passed .through the y.reactor 9 zpoundsof the catalyst'prepared as above Were introduced while maintainedfin an atmosphere of CO2. .The catalyst mass Was'then Vheated 'gto approximately .400" by heating the .Water .bath in 'gjacket .11. During .this ,time the catalyst :Was .aerated with .sm-all streams of untilthetemperature reached BOOIfF. Thenihydrogen '.Was .used fas zthe :aerating medium l.until the admission of .feed gas. After-the catalyst mass .had :been heated :to the desired reaction temperature ,the i introduction 'of preheated :feed gas :Was-initiated. `Conversion fstarted substantially .immediately and :the operaticn `fwas v.ccntinue'd; foraY some time Qduringzwhich :the temperature lwas controlledbyxthe Water .bath vin jacket 1I. Then the .Water Vwas .Withdrawnirom jacket y1| and the rtemperaturexintthe catalystrbedxwas controlled by the introduction through nozzles 84, 85 and 86 of a naphtha, produced by the reduction of carbon monoxide with hydrogen, boiling between 126 and 360 F., and containing 16.6% mono-olens. The connections between conduits 'I9 and 86 and the recovery system were reversed every 15 minutes and the catalyst lter not in use was blown back by the passage of tail gas therethrough in the reverse direction. The conditions observed and the results obtained during two periods of this operation are set forth in the following table under columns A and B.

A B C Hours on condition 18 12 30 Operating Conditions Average temperatures F.:

8.5 ft. above pipe 73. 422 417 389 6.5 ft. above pipe 73. 431 416 398 4.5 it. above pipe 73. 446 440 406 2.5 ft. above pipe 73. 407 404 410 1.5 ft. above pipe 73 324 320 414 0.5 ft. above pipe 73 268 265 414 Charge gas temperature, F 402 406 414 Pressure (pounds/sq. in.-Outlet) 25 25 25 Bed conditions:

Bed height, in feet 8.2 8.0 7. 3 Catalyst density (pounds/cu. ft.)... 53 54 46 Velocity (ft/sec. at the inlet) 0.47 0.44 0. 62 Cu. ft. inlet gas/hr./cu. ft. catalyst.. 398 376 585 Liters inlet gas/hr./gram cobalt.-... 1. 41 1. 30 1. 9 Throughputs:

Gas entering catalyst bed (std. cu.

ft. 1, 182. 2 727. 3 2, 583. 9 Gas leaving catalyst bed (std. cu.

ft. 643. 5 368. 7 l, 139.8 Blow back gas to lter (std. cu. ft./

hr.) 13. 4 11.4 14. 4 Cos. of cooling liquid injected per hr. (at 70 F.):

Through nozzle 84 l, 025 960 0 Through nozzle 85...- 845 2, 705 Through nozzle 86 0 0 Analysis of Charge gas (air free) Per cent CO3 7. 7 1.1 6.0 Per cent CO..- 25.3 27.0 24. 7 Per cent HL--- 62. 2 66.3 60. 5 Per cent CH4 3. 9 4. 7 8. 0 Per cent N2. 0. 1 0. l Per cent H2O.. 0.8 0. 8 0.8

i Results Per cent CO reacted 67. 5 71. 6 76.0 Per cent CO converted to methane and ethane 23. 1 27. 2 2l. 7

The above data indicate that While substantial conversion of the reactants occurred with the development of suicient heat of reaction to require the injection of the large amount of cooling liquid indicated the catalyst temperature Was maintained within the required degree of uniformity and the uidized condition of the catalyst was not aiected by the liquid injected into the reactor and vaporized therein. The measure of temperature control is indicated by the small proportion of the CO which was converted to methane and ethane while reacting a large proportion of the CO in the charge gas. The low temperature near the bottom of the reactor ap-l parently was caused by heat losses from the lower part of the reactor and pipe 73. The velocity in the foregoing table is based on feed plus vaporized oil injected through pipe 84.

For purposes of comparison the results obtained from a similar operation in which temperature was controlled entirely by means of the presence of cooling water in jacket 'H are given in the above table under column C. In the operation represented by column C Water under a pressure of 204 pounds per square inch was maintained in jacket 'Il to provide a water bath at a tage in favor of the direct injection method i since it is not dependent upon the use of a reaction zone of small diameter whereas the method represented by column C is dependent upon the use of a. small diameter reaction zone as exemplied by reactor l0. That the operations represented by columns A and B provided good control of the reaction temperature is shown by the low conversion Yof carbon monoxide to methane and ethane obtained in these operations and the relatively uniform temperatures in the dense phase of the catalyst zone.

It should be noted that in the period of operation of column A, cooling liquid was injected about 4 feet above the interface of the dense phase through nozzle 86 to quench the reaction mixture and to aid in removal of entrained catalyst from the reaction effluent.

Example II Weight Per Size Range ent 40| Trace 40/60 5. 0 60/80 6. 9 /100 4. 0 10o/120 1. 0 12o/140 9. 4 14o/200 12. 9 20D/pan 60. 8

The supported cobalt catalyst was reduced with hydrogen at a temperature of about '7007 F'. in reactor I0 using Dowtherm as the heat control uid in jacket 1I. The catalyst composition Was Co:2 Superltrol. The Dowtherm was removed from jacket il and replaced with water at a temperature equivalent to a, catalyst temperature of 300 F. The introduction of feed gas was then initiated and the temperature was raised rapidly to 400 F. The iioW of the reaction product through conduits 'i9 and 80 was reversed every 15 minutes and the catalyst lter not in use was blown back by the passage of tail gas therethrough in the reverse direction. This operation was continued for some time, during which the temperature was controlled by the water bath in jacket 1|. Then the water was removed from the jacket and the temperature in the catalyst bed was controlled by the introduction of water through nozzles 84, and S6. The conditions observed and the results obtained during a period of this operation are set forth in the following table under column D. In column E of the following table there are set forth the conditions and results of a comparable operation in Which temperature control was obtained entirely by means of a. water bath in jacket 'l l, the water bath being held under a pressure of 307 pounds 3Hoxirs on condition .T..,..-.V.. f 6 24 Operating conditions Average temperatures, '635 feet above pipe 73.. 420 433 4.5 feet above pipe 73.- .A 435 440 427` 443 424 448 422 450 28oA 77 Bed height'in feet 5, 5 Catalyst density (pounds/cu. ft.).. 49 Superficial veolocityy (fn/sec., at the 0.75 Cu. ft. 1nlet,` gas/hrl /cu, itl catalyst y 1,1,70 nLlters inlet; gas/hn/grain cobalt... 3: 7 '5. 0 Throughputsz Y l 'Gas'entering ataly 7 lbed std. cu. ft.)-. .57.3, 3 3,168.0 .Gasleaving catalyst bed (std. cu. t.).'. '422.1 l', 980; 6 Blow-back gas to Afilter 4(std. cu ft./hr.).. 14.1 10.4

Ges. otwater injected per l1our'(at.70"y F.) i

:Through nozzle 84.. 220' 0 :Through nozzle. 85 150 '0 rThrough nozzle 186.. y 110` 0 Anatysis of charge aas' (nir free) Per cent CO2 y2l. 0 Percent CO.- f25. 3 30.0 Pergent 3314..-.-. 66.4 61.7 Per cent CHA-N2. 44. 2 A4. 5 Perceel H20-funn.' fsf 1?".-'.:"".'', '0;8 0'8 "Results Pof "rit `CMO i'actedx.; 1....-; .233 46 Per ent Cra-convertedtomethane'andetliane "310 f'll4 flh'eabove Ydataindicates that While substantial conversion of thereactants l occurred with the'developmentoffsufcient heat `of reaction to require the injection of substantial amounts of w'ater the catalyst temperature was "maintained within therequired degree of vuniforrn'ity.and lthe fluidized pcondition of the` catalyst was not aifectedvby the water injectedminto the reactor and vaporized therein. The measure of temperature control lin the operation jofcolumn Dfis indicated by the smallproportion ofv carbon monoxide which Iwas vconverted to,"methane and, ethane and bythe uniform temperatures inthe catalyst bed.

ln the periodof operation'oitcolumn D, water was'injectedthroughnozzles 85'and 86 at adistance of "about one half foot .and about five feet, respectivelyabove the interface of the dense phase in reactor 10. -As is evident Vfrom the table shown by comparison of the temperature at 6.5 feet above pipe l'I3 of columns D and El, theinjection of -vater through nozzle n85` above the denser'phase lresulted in lovvering of the temperature of more than twice that AWhich 'occurred when no liquid was injected above the dense phase. The quenching of theefiluentfgas from the dense phase inths Vrfarmer 'accounted inat hasta-*substantial vpart-for Ythe marked-decrease in carbon monoxidefconverted 'to methane rand ethane for the period yof column lD as compared to `the period of operation vof column'E.

--In vthe operations `ol?Exainples I "andII the control of the 'temperature of Vthe catalyst mass, in theoperations exemplifying the invention, was effected Aentirely by the injection of "cooling fluid which Waseither naphtha'or water. While this method of 'temperature control vvliasfbeen;shown to rbe sucient the invention @includes lvvithin f its scope falso the use of Ithe liquid inectionlm'ethod of temperaturecontrol inlco'mbinationvvith lother control methodsY such as -indirect heat exchange of cooling fluid with vthe "catalyst lmas's. The

llattenmethod vof operation is illustrated by lthe following example involvingoperations in which the reactor 10 was surrounded by a water bath in jacket H and in which cooling was effected by the injection of a suflicient quantity of water to'absorbthe exothermic heat of the reaction as 'sensible heat and as heat of vaporization.

Example III The vsame catalyst used in Example II was em- "ployed in this example. However, in the operation represented by column D of Example `4II jacket 'll was empty whereas in this example jacket 1l contained Water maintained undera Lpressure equivalent to a temperature of .426 F.

The operating conditions and results obtained in Vselected periods from two separate operations of rthis general nature are set forth in'the following table:

vF 'G Hours onfconditon 12 5 Operating conditions Average temperatures, F.: l

6.5 feet above pipe 73 433 431 4.5 feet above pipe 73... 435 432 z 5 feet above pipe 73 430v 430 1 5 feet above pipe 73. 319 352 0.5 feet above pipe 73. 414v 310 Charge gas temperature..-. 73, 70 Pressure (pounds per square v s 48. 5 V'47. 5 A ,Y ,Y Y 45.0 V44.6 Bed'coudition'sz` v Bed height in'feet 5, o 5, 0 "Catalyst density (pounds/cu. it.).. v53 54 =`Supercial velocity (ftJscc. at the inlet). o, 67 o, 51 Cu. ft. inlet gas/hr./cu. ft.- catalyst 935 981 vLiters ixlet gas/hr./gram cobalt 3, 67 3, 71 Throu 11 s:

Gags entering catalyst bed (std. cu. ft.) 1y 151 582; 6 Gas leaving catalyst bed (std. cu. ft.). .767. 3 370, 8 5 Blowback gas to filter (std. cu. ft./hr. '17, 0 25, 6

Ccs. of water injected per hours (at 70 E):

Through nozzle 84 662 Y Through nozzle 85... k0 70e Through nozzle 86 0 'Analysis of Charge gas (air and H20 free) 4.1 2. 0 30.0 28. 5 60.8 65.2 4.0 4 0 Per cent NL-.. 1. l 0.3

Results Per cent CO reacted 32.1 4l. 6 Per cent CO converted to methane and ethane... 7 2. 0 10. 4

Satisfactory control of the reaction temperature in the operations represented by columns F and G, of the foregoing table is indicated by the direct temperature measurements in the reactor and by the low percentage of the carbon monoxide feed Which Was converted to methane and ethane. It willbe noted that in the operation represented by column F al1 ofthe water was injected through nozzle 8d near the .bottom of the reactor whereas in` theoperation of column G thewaterwas distributed more uniformly by injection through all three nozzles. Since the amount of water injected in these operations was approximately equivalent to the vamount, necessary toabsorb all the heat of reaction by vaporization thereof and since complete vaporization did occur it is evident that the presence of the heated Water bath around reactor 'lli was effective principally to preventJ cooling of the reaction zone by radiation, etc. In the single tube apparatus of Fig. 2 the ratio of surface to volume is much larger than it would be in a larger reactor of the type which would be employed in commercial practice. The heated Water bath at a temperature of 426 F. around the gases issuing from the dense phase apparently eiectively prevented any substantial cooling of the gases by injection of liquid above the interface of the dense phase as in Examples I and II.

The increased production oi methane and ethane in the period of operation of column G was probably due to the higher average temperature of the dense phase than that of column F.

The invention has been illustrated by reference to the use of reactors of large cross-sectional area containing a sing1e mass of catalyst and by reference to the use of reactors in which the catalyst mass is contained in one or more of a plurality of tubes of relatively small cross-sectional area. The rst type of reactor is exemplified by reactor VIl) of Fig. 1 and the second type of reactor is exemplied by Fig. 2. It will be understood that while the reactor of Fig. 2 is limited to a single tube, because of limitations on the size of apparatus for experimental use, the principles of operation illustrated thereby are directly applicable to a larger reactor made up of a plurality of tubes of the same or larger diameter in a common zone in which they may be in contact with a water bath in addition to being cooled by directl injection or in which they may be cooled entirely by the latter method.

While the tubular type of reactor exemplified by Fig. 2 may appear to involve the use oi a catalyst mass of relatively small cross-sectional area the diameter of the tube comprising reactor 'm in Fig. 2 is, nevertheless, substantially greater than the tubes in tubular reactors employing a xed catalyst bed. In the latter the maximum diameter of the tubes is approximately 1A; that of reactor 10 whereby the tubes employed have a crosssectional area of approximately that of reactor 10.

The cooling iiuid which is injected into the reactor and into contact with the catalyst mass preferably is distributed in the reactor zone in a manner to permit substantially instantaneous vaporization of the liquid and prevent the accumulation of liquid 'in any part of the reaction mass. The latter result is undesirable since it may cause an agglomeration of catalyst particles into large masses whereby the iiuidized nature of the catalyst mass would be impaired. In a reaction zone of large cross-sectional area in which the catalyst circulates at a rapid rate throughout the reaction zone the distribution of the cool liquid in the reaction zone is carried out largely by the catalyst itself. On the other hand in reactors in relatively small cross-sectional areas such as Fig. 2, in which vertical circulation of catalyst is less eiective it is more important to provide for proper distribution of cooling fluid by injection at a plurality of points as illustrated.

Having described my invention, I claim:

1. In a process for the hydrogenation of a carbon oxide to produce organic compounds, including methane, by passing the reactants through a mass of finely-divided contact material comprising a mixture of catalyst particles of varying particle size, a substantial portion of which particles has free settling rates less than the superficial velocity of the gases passing through the reactor, under conditions f gas velocity such that a lower relatively dense pseudoliquid phase and an upper relatively dilute phase of contact material is formed with an interface therebetween and further characterized by the entrainment of a substantial proportion of the contact material in the dilute phase at the gas velocities employed, the method. f01

minimizing entrainment of contact material in the dilute phase and suppressing the formation of methane which comprises injecting into said dilute phase above said interface a liquid which is substantially free from solids and completely vaporizable at the reaction conditions.

2. The process of claim 1 in which said liquid comprises a hydrocarbon.

3. The process of claim 1 in which said liquid is an organic liquid previously produced as a product of the process.

4. The process of claim 1 in which said liquid is water.

5. The process of claim 1 in which said liquid at the time of injection is at a temperature substantially below its boiling point at the reaction conditions.

6. A process for hydrogenating a carbon oxide which comprises continuously flowing a gaseous mixture comprising hydrogen and a carbon oxide upwardly in a reaction Zone through a mass of iinely divided contact material comprising a catalyst for the reaction and at the reaction temperature to maintain the body of contact material substantially in suspension, limiting the upward linear velocity of the gaseous mixture and the bulk of the contact material to form a lower relatively dense pseudo-liquid phase of the greater part of the mass of contact material in which the particles of contact material circulate at a relatively high rate and an upper relatively dilute phase of contact material, said dense phase and said dilute phase forming an interface therebetween, maintaining the upward velocity of the gaseous mixture higher than the free settling rate of particles comprising a substantial proportion of said dense phase whereby contact material is entrained in the gaseous reaction mixture passing from said dense phaseI directly injecting into said dilute phase adjacent said interface a liquid which is substantially free from solids and completely vaporizable at the reaction conditions whereby a substantial proportion of said entrained contact material isdisengaged and falls back into said dense phase. and withdrawing a gaseous reaction mixture and vaporized liquid from said reaction zone to recover reaction products therefrom.

'7. A process for nydrogenating carbon monoxide which comprises continuously owing a gaseous mixture comprising hydrogen and carbonmonoxide upwardly in a reaction zone through a mass of finely divided contact material comprising a catalyst for the reaction and at the' reaction temperature to maintain the body of contact material substantially in suspension and to produce normally liquid organic compounds', limiting the upward linear velocity of the gaseous mixture and the bulk of the contact material such that a relatively dense pseudo-liquid phase of the greater part of the mass of contact mareaction gases passing from said dense phasel to a substantially lower temperature whereby' the formation of normally gaseous hydrocarbons' is minimized, and withdrawing a gaseous reaction mixture and vaporized liquid from the upper portion, of said reaction zone to recover normally liquid reaction products therefrom.

8. rIhe process of claim 'l in which said catalyst comprises cobalt supported on acid treated bentonite.

9. The process of claim 7 in which said catalyst comprises reduced iron.

i0. A process for the hydrogenation of carbon monoxide which comprises continuously flowing a gaseous mixture comprising hydrogen and caroon monoxide upwardly in a reaction Zone through a mass of finely divided contact material comprising a catalyst for the reaction at the reaction temperature to maintain the body of contact material substantially in suspension, limiting the upward velocity of the gaseous mixture to maintain the greater part of the mass of contact material in a relatively dense pseudoliquid phase in which the particles of contact material circulate at a relatively high rate, providing a contact mass oi suiicient bulk to produce a dense phase deep enough to afford a length of time of contact between the gaseous reactants and the catalyst effective to react a substantial proportion of said carbon monoxide with hydrogen to produce normally gaseous and liquid hydrocarbons, withdrawing a gaseous reaction mixture comprising unreacted hydrogen and hydrocarbons from said reaction zone, in a rst condensation step cooling said effluent to condense hydrocarbons boiling above the gasoline range and removing same from said eiiluent, in a second condensation step cooling the uncondensed eilluent from said rst condensation step to condense a portion thereof, passing the cooled eiiluent from said second condensation step to an accumulation zone, passing uncondensed 'vapors comprising C3 and C4 hydrocarbons and unreacted hydrogen from said accumulation zone to an absorption zone, contacting said vapors in said absorption zone with a liquid hydrocarbon to absorb Cs and C4 hydrocarbons therein, stripping absorbed hydrocarbons from the enriched liquid hydrocarbon from said absorption Zone, cooling and condensing the hydrocarbons thus recovered and passing same to said accumulation zone, removing condensate from said accumulation zone and injecting said condensate into said reaction zone.

l1. The process of claim l0 in which -said 'condensate from said accumulation zone is passed to a debutanizer in which a relatively low-boiling fraction comprising C4 hydrocarbons and a relatively high-boiling fraction comprising hydrocarbons boiling in the gasoline range are removed therefrom, separating an intermediate liquid fraction from said debutanizer and injecting said n intermediate fraction into said reaction zone.

l2. A process for the hydrogenation of carbon monoxide which comprises continuously nowing a gaseous mixture comprising hydrogen and carbon monoxide upwardly in a reaction zone through a mass of finely divided contact material comprising the catalyst for the reaction and at the reaction temperature to maintain the body of contact material substantially in suspension to produce normally gaseous and liquid hydrocarbons, limiting the upward linear velocity of the gaseous mixture and the bulk of the contact material to form a lower relatively dense pseudoliquid phase of the greater part of the mass of contact material and an upper relatively dilute l ffl phase of contact material, removing a gaseous reaction eiluent from said reaction zone, cooling and condensing said reaction eliiuent, passing the cooled and condensed eiiluent to an accumulation zone in which condensate is separated from uncondensed vapors, passing uncondensed vapors from said accumulation Zone to an absorption zone, contacting said uncondensed vapors in said absorption zone with an absorption medium to recover the relatively high-boiling components `of said vapors, cooling and condensing said recovered relatively high-boiling components and passing same to said accumulation zone, passing condensate from said accumulation zone to a fractional distillation zone in which a relatively low-boiling and a relatively high-boiling fraction are removed therefrom, withdrawing an intermediate boiling liquid fraction from said fractional distillation zone, and injecting said intermediate boiling liquid fraction into said re'- action zone to cool the reaction zone and maintain a substantially constant temperature therein.

13. The process of claim l() in which said intermediate boiling liquid fraction is injected into the dilute phase of said reaction Zone whereby entrained contact material is disengaged and falls back into said dense phase and the reaction mixture passing from said dense phase is quenched.

14. A process for the hydrogenation of carbon monoxide which comprises continuously iiowing a gaseous mixture comprising hydrogen and carbon monoxide upwardly in a reaction zone through a mass of iinely divided contact material comprising the catalyst for the reaction and at the reaction temperature to maintain the body of contact material at least in suspension to produce normally gaseous and liquid hydrocarbons, removing a gaseous reaction efuent from said reaction zone, cooling and condensing said reaction eilluent, passing the cooled and condensed effluent to an accumulation zone in which condensate is separated from uncondensed vapors, passing uncondensed vapors from said accumulation zone to a recovery zone, recovering relatively high-boiling components of said vapors from the aforesaid condensation step, cooling and condensing the thus recovered relatively high-boiling components and passing saine to said accumulation zone, passing condensate from said accumulation zone to a fractional distillation zone in which a relatively low-boiling and a relatively high-boilng fraction are removed therefrom, withdrawing an intermediate boiling liquid fraction from said fractional distillati-on zone, and injecting said intermediate boiling liquid fraction into said reaction zone to cool the reaction Zone and maintain a substantially constant temperature therein.

LOUIS C. RUBIN.

REFERENCES CITED The following references are of record in the ille of this patent:

UNITED STATES PATENTS Number Name Date 1,984,380 Odell Dec. 18, 1934 2,379,734 Martin July 3, 1945 2,496,851 Redcay Sept. 3, 1946 2,424,467 Johnson July 22, 1947 2,447,505 Johnson Aug. 24, 1948 2,474,583 Lewis, Jr June 28, 1949 

1. IN A PROCESS FOR THE HYDROGENATION OF CARBON OXIDE TO PRODUCE ORGANIC COMPOUNDS, INCLUDING METHANE, BY PASSING THE REACTANTS THROUGH A MASS OF FINELY-DIVIDED CONTACT MATERIAL COMPRISING A MIXTURE OF CATALYST PARTICLES OF VARYING PARTICLE SIZE, A SUBSTANTIAL PORTION OF WHICH PARTICLES HAS FREE SETTLING RATES LESS THAN THE SUPERFICIAL VELOCITY OF THE GASES PASSING THROUGH THE REACTOR, UNDER CONDITINS OF GAS VELOCITY SUCH THAT A LOWER RELATIVELY DENSE PSEUDOLIQUID PHASE AND AN UPPER RELATIVELY DILUTE PHASE OF CONTACT MATERIAL IS FORMED WITH AN INTERFACE THEREBETWEEN AND FURTHER CHARACTERIZED BY THE ENTRAINMENT OF A SUBSTANITAL PROPORTION OF THE CONTACT MATERIAL IN THE DILUTE PHAST AT THE GAS VELOCITIES EMPOLYED, THE METHOD FOR MINIMIZING ENTRAINMENTOF CONTACT MATERIAL IN THE DILUTE PHASE AND SUPPRESSING THE FORMATION OF METHANE WHICH COMPRISES INJECTING INTO SAID DILUTE PHASE ABOVE SAID INTERFACE A LIQUID WHICH IS SUBSTANTIALLY FREE FROM SOLIDS AND COMPLETELY VAPORIZABLE AT THE REACTION CONDITIONS.
 10. A PROCESS FOR THE HYDROGENATION OF CARBON MONOXIDE WHICH COMPRISES CONTINUOUSLY FLOWING A GASEOUS MIXTURE COMPRISING HYDROGEN AND CARBOND MONOXIDE UPWARDLY IN A REACTION ZONE THROUGH A MASS OF FINELY DIVIDED CONTACT MATERIAL COMPRISING A CATALYST FOR THE REACTION AT THE REACTION TEMPERATURE TO MAINTAIN THE BODY OF CONTACT MATERIAL SUBSTANTIALLY IN SUSPENSION LIMITING THE UPWARD VELOCITY OF THE GASEOUS MIXTURE TO MAINTAIN THE GREATER PART OF THE MASS OF CONTACT MATERIAL IN A RELATIVELY DENSE PSEUDOLIQUID PHASE IN WHICH THE PARTICLES OF CONTACT MATERIAL CIRCULATE AT A RELATIVELY HIGH RATE, PROVIDING A CONTACT MASS OF SUFFICIENT BULK TO PRODUCE A DENSE PHASE DEEP ENOUGH TO AFFORD A LENGHT OF TIME OF CONTACT BETWEEN THE GASEOUS REACTANTS AND THE CATALYST EFFECTIVE TO REACT A SUBSTANTIAL PROPORTION OF SAID CARBON MONOXIDE WITH HYDROGEN TO PRODUCE NORMALLY GASEOUS AND LIQUID HYDROCARBONS WITHDRAWING A GASEOUS REACTION MIXTURE COMPRISING UNREACTED HYDROGEN AND HYDROCARBONS FROM SAID REACTION ZONE, IN A FIRST CONDENSATION STEP COOLING SAID EFFLUENT TO CONDENSE HYDROCARBONS BOILING ABOVE THE GASOLINE RANGE AND REMOVING SAME FROM SAID EFFLUENT, IN A SECOND CONDENSATION STEP COOLING THE UNCONDENSED EFFLUENT FROM SAID FIRST CONDENSATION STEP TO CONDESE A PORTION THEREOF, PASSING THE COOLED EFFLUENT FROM SAID SECOND CONDENSATION STEP AN ACCUMULATION ZONE, PASSING UNCONDENSED VAPORS COMPRISING C3 AND C4 HYDROCARBONS AND UNREACTED HYDROGEN FROM SAID ACCUMULATION ZONE TO AN ABSORPTION ZONE, CONTACTING SAID VAPORS IN SAID ABSORPTION ZONE WITH A LIQUID HYDROCARBON TO ABSORB C3 AND C4 HYDROCARBONS THEREIN, STRIPPING ABSORBED HYDROCARBONS FROM THE ENRICHED LIQUID HYDROCARBON FROM SAID ABSORPTION ZONE, COOLING AND CONDENSING THE HYDROCARBONS THUS RECOVERED AND PASSING SAME TO SAID ACCUMULATED ZONE, REMOVING CONDENSATE FROM SAID ACCUMULATION ZONE AND INJECTING SAID CONDENSATE INTO SAID REACTION ZONE. 